[go: up one dir, main page]

US2507766A - Production of alkyl benzenes - Google Patents

Production of alkyl benzenes Download PDF

Info

Publication number
US2507766A
US2507766A US753562A US75356247A US2507766A US 2507766 A US2507766 A US 2507766A US 753562 A US753562 A US 753562A US 75356247 A US75356247 A US 75356247A US 2507766 A US2507766 A US 2507766A
Authority
US
United States
Prior art keywords
benzene
alkylation
zone
olefins
alkylation zone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US753562A
Inventor
Fredrick M Smith
Robert S Hanmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to US753562A priority Critical patent/US2507766A/en
Application granted granted Critical
Publication of US2507766A publication Critical patent/US2507766A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/70—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C07C2527/12—Fluorides
    • C07C2527/1206—Hydrogen fluoride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/901—Catalyst and recycle considerations with recycle, rehabilitation, or preservation of solvent, diluent, or mass action agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/901—Catalyst and recycle considerations with recycle, rehabilitation, or preservation of solvent, diluent, or mass action agent
    • Y10S585/902—Recycle of solvent and catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/954—Exploiting mass-action phenomenon

Definitions

  • Tins invention relates to an improved process for the production of high molecular weight alkyl aromatics.
  • One embodiment of this invention relates to an improved process for the alkylation of aromatic hydrocarbons with high molecular weight oleiins in the presence of hydrogen fluoride as catalyst.
  • this invention relates to the alkylation of benzene with high molecular weight straightand branched-chain olefins in the presence of a hydlcgen fluoride catalyst wherein increased yields of useful alkylate and lower catalyst consumption are achieved through improvements in separatlon of catalyst from the reaction eflluent.
  • an aromatic hydrocarbon and an olefin concentrate alkylating reactant are agitated with a liquid type catalyst such as hydrogen fluoride under conditions suitable for the condensation of the olefins present in the concentrate with the aromatic hydrocarbon contained therein
  • a liquid type catalyst such as hydrogen fluoride
  • the alkylation efliuent is passed to a separating chamber where it is divided into catalyst and hydrocarbon phases by gravity, the heavier catalyst phase being returned to the alkylation zone and the hydrocarbon phase discharged for fractionation.
  • catalyst-soluble products remain in the higher-boiling fraction and as the stream is further fractionated are separated in a manner such that alkyl aromatics previously held in the catalyst phase are discharged as product while higher boiling olefin polymers and polyalkyl aromatics remain as bottoms.
  • These bottoms products can be utilized by recycling to the alkylation zone where conditions favor depolymerization of the polymers and side-chain transfer from the polyalkyl aromatics to unalkylated aromatic hydrocarbons, thus efiecting a high degree of utilization of products formerly held in the catalyst phase and removed as waste in the catalyst regeneration.
  • 0ne object of this invention is to provide an improved process for the production of alkyl aromatics.
  • Another object of this invention is the alkylation of aromatic hydrocarbons with high molecular weight olefins in the presence of hydro gen fluoride catalyst.
  • Still another object is to substantially reduce the formation of catalyst-soluble products formed in alkylation of aromatic hydrocarbons with high molecular weight olefins.
  • Still another object is to substantially reduce catalyst consumption in the alkylation of aromatic hydrocarbons with high molecular weight olefins.
  • Another object is to provide an improved process for the production of alkyl benzenes suitable f or use as detergent intermediates.
  • a specific object of this invention is to provide an improved catalytic process for alkylating benzene with oleflns containing at least seven and not more than eighteen carbon atoms to the molecule.
  • a high molecular weight oleflnic material which may preferably be an olefin concentrate which also contains other hydrocarbons as well, is passed from storage I through line l2 to alkylation zone M 'where it is mixed with benzene which is drawn from storage [8 through line l8 and/or from recycle line and hydrogen fluoride catalyst which is drawn from storage 22 through line 24 and/or contained in the recycle stream from line 20.
  • reaction mixture is agitated by mechanical stirrer 26 while conditions in the alkylation zone are maintained to give a high degree of conversion of olefin to alkyl benzenes.
  • eiiluent is discharged through line 28 to fractionator 30, which should be lined with an acid resistant material, such as Monel metal, where hydrogen fluoride and unreacted benzene are removed overhead for recycle to the alkylation zone through line 20.
  • acid resistant material such as Monel metal
  • Hydrocarbons boiling above benzene and below the alkyl benzenes which may be present in the alkylation zone eilluent are removed through line 32 for storage or utilization elsewhere. Such hydrocarbons may be contained in the olefin concentrate introduced through line l2.
  • the kettle product is passed through line 34 to fractionator 38, which will preferably be operated at reduced pressure.
  • fractionator 38 which will preferably be operated at reduced pressure.
  • a fraction boiling in the range 500 to 700 F. (corrected to atmospheric pressure), and comprising a mixture of mono alkyl benzenes valuable for use as detergent intermediates is removed via line 38.
  • the highboiling olefin polymers and polyalkyl benzenes may be recycled to the alkylation zone through lines 42 and H or may be discharged from the system through line ii if desired.
  • this material is recycled, we have found that substantial recovery of useful material is possible since under the conditions maintained in the reactor, the olefin polymers tend to depolymerize to supply olefins utilizable in the alkylation rial may be withdrawn from fractionator 36 through line 40.
  • the catalyst to be employed in the process of our invention is hydrogen fluoride, either in substantially anhydrous form or in aqueous solutions of 50 per cent or higher concentration.
  • the quantity used may be as low as ten per cent of the total volume of the reaction mixture although optimum results will generally be obtained with slightly larger amounts, say from 15 to 30 per cent. Larger amounts may be employed when desired.
  • the olefins to be employed in the process of our invention contain at least seven and not more than eighteen carbon atoms to the molecule and may conveniently be supplied as olefin concentrates.
  • Convenient and economical sources of such concentrates lie in selected fractions of cracked petroleum naphthas which come within a boiling range between 200 and 600 F.; for example, a cracked naphtha from a Cycloversion" process may be employed, such as is described in the Oil and Gas Journal, April 13, 1944 by Schulze et al.
  • a thermally cracked naphtha may be employed if desired.
  • Temperatures in the alkylation zone should generally be in a range between about 60 and about 120 F., but preferably between 75 nd F.
  • the reaction can be effected without the use of superatmospheric pressures, but it is generally desirable to apply adequate pressure to avoid vaporization of the catalyst. For example, from 30 to 50 pounds per square inch gauge is satisfactory.
  • the mol ratio of aromatic to olefin entering the alkylation zone should be between 2:1 and 15:1, but preferably from 5:1 to 10:1.
  • the rate of flow of the reaction mixture is such that the residence time in the alkylation zone is in the range of about 5 to about 60 minutes, however a range of 15 to 45 minutes is preferable.
  • the process of our invention is applicable to the alkylation of benzene, toluene, the xylenes, and the like, but it is particularly adaptable to the alkylation of benzene with high molecular weight olefins.
  • the use of selected fractions of highly aromatic petroleum naphtha may be employed as a source of alkylatable aromatic hydrocarbons.
  • Example I An olefin feed stock boiling from 400 to 456 F. was prepared by fractionating a naphtha made by thermally cracking a topped crude. Analysis of said feed showed an olefin content of 30 per cent and aromatic constitutents amounting to 16 per cent.
  • the oleflnic stock was fed to two reactors where it was combined with benzene in a ratio of 1 mol of olefin to 8 mols of benzene.
  • the hydrogen fluoride catalyst wa added to both reactors. In the first reactor, hereinafter designated as reactor A, the catalyst was added to an extent of 24 per cent of the total volume. In the second reactor, designated as reactor B, the catalyst was added to an extent of 50 per cent of the total volume.
  • An improved process for catalytically producing high molecular weight alkyl benzenes which comprises mixing alkylatable benzene hydrocarbons and olefin-bearing material containing olefins having at least seven and not more than eighteen carbon atoms per molecule with hydrogen fluoride in an alkylation zone; maintaining a temperature in said alkylation zone in the range of about 60 to about 120 F.; maintaining a pressure in said alkylation zone suflicient to prevent vaporization of said hydrogen fluoride; maintaining the rate of feed of said olefin-bearing material and said benzene hydrocarbons such that the residence time in said alkylation zone is in the range of about 5 to about 60 minutes; maintaining a mol ratio of said benzene hydrocarbons to said olefin entering said alkylation zone in the range oi about :1 to about 2:1; introducing the entire eiiluent reaction mixture which contains polymers of said oleflns having at least 7
  • said fractionation zone hydrocarbon material boiling above said unreacted benzene hydrocarbons and boiling below the alkyl benzene-bearing material, introducing the remaining higher boiling alkyl benzene-bearing material from said fractionation zone to another fractionation zone, removing an alkyl benzene fraction from said higher-boiling alkyl benzene-bearing material, and recycling at least a portion of the remaining higher-boiling material which contains the said polymers of said olefins and said undesired polyalkyl aromatics to said alkylation zone wherein depolymerization of said polymers of said olefins and side-chain transfer from the said undesired polyalkyl aromatics resulting in desirable alkylation of benzene by the depolymerized olefins and the side-chains from the undesired polyalkyl benzenes is caused to occur simultaneously with the alkylation in said alkylation zone of the benzene by said
  • An improved process for catalytically producing high a molecular weight alkyl benzenes which comprises mixing benzene and olefin-containing material obtained from a cracked naphtha having a boiling range of 200 to 600 F. with hydrogen fluoride in an alkylation zone; maintaining a temperature in said alkylation zone in the range or about 60 to about F.; maintaining a pressure in said alkylation zone suflicient to prevent vaporization of said hydrogen fluoride catalyst; maintaining the rate of feed of olefin-bearing material and benzene such that the residence time in said alkylation zone be in the range of about 5 to about 60 minutes; maintaining a mol ratio of benzene to olefln entering said alkylation zone in the range of about 15:1 to about 5:1; introducing the entire efliuent reaction mixture which contains polymers of said olefins having at least '7 carbon atoms per molecule which normally are dissolved in said hydrogen fluoride as well

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented May 16, 1950 UNITED STATES PATENT OFFICE PRODUCTION OF ALKYL BENZENES Application June 9, 1947,, Serial No. 753,562
2 Claims. l
Tins invention relates to an improved process for the production of high molecular weight alkyl aromatics. One embodiment of this invention relates to an improved process for the alkylation of aromatic hydrocarbons with high molecular weight oleiins in the presence of hydrogen fluoride as catalyst. In one specific embodiment this invention relates to the alkylation of benzene with high molecular weight straightand branched-chain olefins in the presence of a hydlcgen fluoride catalyst wherein increased yields of useful alkylate and lower catalyst consumption are achieved through improvements in separatlon of catalyst from the reaction eflluent.
According to one prior method an aromatic hydrocarbon and an olefin concentrate alkylating reactant are agitated with a liquid type catalyst such as hydrogen fluoride under conditions suitable for the condensation of the olefins present in the concentrate with the aromatic hydrocarbon contained therein The alkylation efliuent is passed to a separating chamber where it is divided into catalyst and hydrocarbon phases by gravity, the heavier catalyst phase being returned to the alkylation zone and the hydrocarbon phase discharged for fractionation.
While this method of operation has numerous advantages, dificulties are encountered in the process as a result of the formation of catalystsolubie products which remain in the catalyst phase. These catalyst-soluble products apparently result largely from the polymerization of clefins, a reaction which is activated by the allsylation catalyst. The olefin polymers combine with the catalyst to form compositions or complexes in which other hydrocarbons, including alkyl aromatics and unalkylated aromatics, are soluble. The element of time is significant in the formation of these catalyst-soluble products, the amount of hydrocarbon so combined being increased with extension in the length of time of contact with the catalyst. The extent of formation of these products is often very large, their volume sometimes exceeding that of useful alkylate produced. Thus a large amount of hydrocarbon otherwise utilizable builds up in the catalyst phase and must be removed from the system continuously to prevent excessive catalyst dilution. Furthermore, when so operating, large volumes of catalyst are required, the amount often being equal to that of the hydrocarbon in the feed.
We have now discovered a process for the production of alkyl aromatics from aromatic hydrocarbons and high molecular weight olefins in the MIL 245M719 presence of a hydrogen fluoride catalyst wherein losses from the formation of catalyst soluble products are eliminated or substantially reduced and much smaller quantities of catalyst are required. According to the method of our invention the alkylation eiliuent is discharged from the alkylation zone directly to the fractionation zone. Here the catalyst, together with unreacted aromatic hydrocarbons, is removed overhead for recycle to the alkylation zone. By operating in this manner, catalyst-soluble products remain in the higher-boiling fraction and as the stream is further fractionated are separated in a manner such that alkyl aromatics previously held in the catalyst phase are discharged as product while higher boiling olefin polymers and polyalkyl aromatics remain as bottoms. These bottoms products can be utilized by recycling to the alkylation zone where conditions favor depolymerization of the polymers and side-chain transfer from the polyalkyl aromatics to unalkylated aromatic hydrocarbons, thus efiecting a high degree of utilization of products formerly held in the catalyst phase and removed as waste in the catalyst regeneration.
0ne object of this invention is to provide an improved process for the production of alkyl aromatics.
Another object of this invention is the alkylation of aromatic hydrocarbons with high molecular weight olefins in the presence of hydro gen fluoride catalyst.
Still another object is to substantially reduce the formation of catalyst-soluble products formed in alkylation of aromatic hydrocarbons with high molecular weight olefins.
Still another object is to substantially reduce catalyst consumption in the alkylation of aromatic hydrocarbons with high molecular weight olefins.
Another object is to provide an improved process for the production of alkyl benzenes suitable f or use as detergent intermediates.
A specific object of this invention is to provide an improved catalytic process for alkylating benzene with oleflns containing at least seven and not more than eighteen carbon atoms to the molecule.
Other objects and advantages of this invention trasted with the fifty volume per cent generally necessary in processes employing gravity separation methods. This lowering in catalyst volume is made possible by the method of our process wherein the catalyst is constantly maintained in a high state of activity, no catalyst-soluble products being returned to the alkylation zone in the recycle. Another advantage of our invention lies in the elimination of expensive catalyst regeneration for removal of catalyst soluble products. A further advantage lies in the high degree of utilization of products formerly lost as waste or at best convertible to useful products only after expensive processing. A still further advantage of our process lies in the immediate and complete separation of the catalyst after the alkylation, thus reducing the contact time to a minimum and thereby correspondingly reducing the formation of catalyst soluble products.
These and other advantages of our invention will be apparent from a description of the accompanying drawing in which is shown a diagrammatic illustration of one specific embodiment of the process. Specific materials are mentioned, not as limiting to the scope of the disclosure, but in the interest of clarity in explanation. Referring to the drawing, a high molecular weight oleflnic material, which may preferably be an olefin concentrate which also contains other hydrocarbons as well, is passed from storage I through line l2 to alkylation zone M 'where it is mixed with benzene which is drawn from storage [8 through line l8 and/or from recycle line and hydrogen fluoride catalyst which is drawn from storage 22 through line 24 and/or contained in the recycle stream from line 20. The reaction mixture is agitated by mechanical stirrer 26 while conditions in the alkylation zone are maintained to give a high degree of conversion of olefin to alkyl benzenes. From the alkylation zone M the eiiluent is discharged through line 28 to fractionator 30, which should be lined with an acid resistant material, such as Monel metal, where hydrogen fluoride and unreacted benzene are removed overhead for recycle to the alkylation zone through line 20. If desired, lowbolling material and/or at least a portion of said hydrogen fluoride and benzene may be removed from the system through line 2|. Hydrocarbons boiling above benzene and below the alkyl benzenes which may be present in the alkylation zone eilluent are removed through line 32 for storage or utilization elsewhere. Such hydrocarbons may be contained in the olefin concentrate introduced through line l2. The kettle product is passed through line 34 to fractionator 38, which will preferably be operated at reduced pressure. Here a fraction boiling in the range 500 to 700 F. (corrected to atmospheric pressure), and comprising a mixture of mono alkyl benzenes valuable for use as detergent intermediates, is removed via line 38. The highboiling olefin polymers and polyalkyl benzenes may be recycled to the alkylation zone through lines 42 and H or may be discharged from the system through line ii if desired. When this material is recycled, we have found that substantial recovery of useful material is possible since under the conditions maintained in the reactor, the olefin polymers tend to depolymerize to supply olefins utilizable in the alkylation rial may be withdrawn from fractionator 36 through line 40.
In the accompanying diagrammatic drawing reference to some of the equipment such as pump '5, gauges, and other equipment which obviously would be necessary to actually operate the process have been intentionally omitted. Only sufficient equipment has been shown to illustrate the process of the invention and it is intended that no undue limitation be read into this invention by reference to the drawing and discussion thereof.
The catalyst to be employed in the process of our invention is hydrogen fluoride, either in substantially anhydrous form or in aqueous solutions of 50 per cent or higher concentration. The quantity used may be as low as ten per cent of the total volume of the reaction mixture although optimum results will generally be obtained with slightly larger amounts, say from 15 to 30 per cent. Larger amounts may be employed when desired.
The olefins to be employed in the process of our invention contain at least seven and not more than eighteen carbon atoms to the molecule and may conveniently be supplied as olefin concentrates. Convenient and economical sources of such concentrates lie in selected fractions of cracked petroleum naphthas which come within a boiling range between 200 and 600 F.; for example, a cracked naphtha from a Cycloversion" process may be employed, such as is described in the Oil and Gas Journal, April 13, 1944 by Schulze et al. A thermally cracked naphtha may be employed if desired.
Temperatures in the alkylation zone should generally be in a range between about 60 and about 120 F., but preferably between 75 nd F. The reaction can be effected without the use of superatmospheric pressures, but it is generally desirable to apply suficient pressure to avoid vaporization of the catalyst. For example, from 30 to 50 pounds per square inch gauge is satisfactory. The mol ratio of aromatic to olefin entering the alkylation zone should be between 2:1 and 15:1, but preferably from 5:1 to 10:1. The rate of flow of the reaction mixture is such that the residence time in the alkylation zone is in the range of about 5 to about 60 minutes, however a range of 15 to 45 minutes is preferable.
The process of our invention is applicable to the alkylation of benzene, toluene, the xylenes, and the like, but it is particularly adaptable to the alkylation of benzene with high molecular weight olefins. In some instances, the use of selected fractions of highly aromatic petroleum naphtha may be employed as a source of alkylatable aromatic hydrocarbons.
Example I An olefin feed stock boiling from 400 to 456 F. was prepared by fractionating a naphtha made by thermally cracking a topped crude. Analysis of said feed showed an olefin content of 30 per cent and aromatic constitutents amounting to 16 per cent. The oleflnic stock was fed to two reactors where it was combined with benzene in a ratio of 1 mol of olefin to 8 mols of benzene. The hydrogen fluoride catalyst wa added to both reactors. In the first reactor, hereinafter designated as reactor A, the catalyst was added to an extent of 24 per cent of the total volume. In the second reactor, designated as reactor B, the catalyst was added to an extent of 50 per cent of the total volume.
Substantially the same reaction conditions were maintained in the two reactors, the temperatures being 90 F., pressures, 30 pounds per square inch gauge, and flow rates such that a contact time of 30 minutes was obtained. The efliuent from reactor A was discharged to a fractionating column where unreacted benzene and catalyst were separated for recycling to the reaction. From reactor B the eilluent was passed to a separator where it was divided into catalyst and hydrocarbon phases by gravity, the hydrocarbon being conveyed to a fractionation system and the catalyst phase recycled to the alkylation reactor. I
Results are tabulated below.
Pounds r Pound of Ole Fed to Reaction Products Reactor Light alkylatc (B. P. BOO-700 F.) l. 023 0. 809 Total alkylate 1. 129 l. 03 Catalyst soluble of! 0.385
Example II Pounds per Pound of Olefin Fed to Reaction Products Reactor Light alkylate (B. P. 500-700 F.) 0. 972 0.421 Total alkylafe 1.154 0. 796 Catalyst soluble il 0. 762
It is to be understood that this invention should not be unnecessarily limited to the above discussion and description and that modifications and variations may be made without departing substantially from the invention or from the scope of the claims.
We claim:
1. An improved process for catalytically producing high molecular weight alkyl benzenes, which comprises mixing alkylatable benzene hydrocarbons and olefin-bearing material containing olefins having at least seven and not more than eighteen carbon atoms per molecule with hydrogen fluoride in an alkylation zone; maintaining a temperature in said alkylation zone in the range of about 60 to about 120 F.; maintaining a pressure in said alkylation zone suflicient to prevent vaporization of said hydrogen fluoride; maintaining the rate of feed of said olefin-bearing material and said benzene hydrocarbons such that the residence time in said alkylation zone is in the range of about 5 to about 60 minutes; maintaining a mol ratio of said benzene hydrocarbons to said olefin entering said alkylation zone in the range oi about :1 to about 2:1; introducing the entire eiiluent reaction mixture which contains polymers of said oleflns having at least 7 carbon atoms per molecule which normally are dissolved in said hydrogen fluoride as well as undesired polyalkyl aromatics from said alkylation zone to a fractionation zone, removing from the upper portion or said tractionation zone a single traction comprising hydrogen fluoride and unreacted benzene hydrocarbons, and recycling at least a portion of said hydrogen fluoride and unreacted benzene hydrocarbons i'raction to said alkylation zone; removing from an intermediate portion 0! said fractionation zone hydrocarbon material boiling above said unreacted benzene hydrocarbons and boiling below the alkyl benzene-bearing material, introducing the remaining higher boiling alkyl benzene-bearing material from said fractionation zone to another fractionation zone, removing an alkyl benzene fraction from said higher-boiling alkyl benzene-bearing material, and recycling at least a portion of the remaining higher-boiling material which contains the said polymers of said olefins and said undesired polyalkyl aromatics to said alkylation zone wherein depolymerization of said polymers of said olefins and side-chain transfer from the said undesired polyalkyl aromatics resulting in desirable alkylation of benzene by the depolymerized olefins and the side-chains from the undesired polyalkyl benzenes is caused to occur simultaneously with the alkylation in said alkylation zone of the benzene by said olefins having at least 7 carbon atoms per molecule.
2. An improved process for catalytically producing high a molecular weight alkyl benzenes, which comprises mixing benzene and olefin-containing material obtained from a cracked naphtha having a boiling range of 200 to 600 F. with hydrogen fluoride in an alkylation zone; maintaining a temperature in said alkylation zone in the range or about 60 to about F.; maintaining a pressure in said alkylation zone suflicient to prevent vaporization of said hydrogen fluoride catalyst; maintaining the rate of feed of olefin-bearing material and benzene such that the residence time in said alkylation zone be in the range of about 5 to about 60 minutes; maintaining a mol ratio of benzene to olefln entering said alkylation zone in the range of about 15:1 to about 5:1; introducing the entire efliuent reaction mixture which contains polymers of said olefins having at least '7 carbon atoms per molecule which normally are dissolved in said hydrogen fluoride as well as undesired polyalkyl aromatics from said alkylation zone to a fractionation zone, removing from upper portion of said fractionation zone a single fraction comprising hydrogen fluoride and unreacted benzene, and recycling at least a portion of said hydrogen fluoride and unreacted benzene fraction to said alkylation zone, removing from an intermediate portion of said iractionating zone hydrocarbon material associated with the original olefin-bearing material, introducing the resulting high boiling hydrocarbon material into a second fractionation zone and removing alkyl benzenes from said high boiling hydrocarbon material and recycling at least a portion of the resulting higher boiling hydrocarbon material which contains the said polymers of said olefins and said undesired polyalkyl aromatics to the alkylation zone wherein depolymerization of said polymers of said olefins and 7 side-chains from the undesired polyalkyl ben- UNITED STATES PATENTS zenes is caused to occur simultaneously with the Number N aikylation in said alkylation zone of the benzene 2 275 312 i g 1942 by said olefins having at least '7 carbon atoms 2349'211 Tuneners et Per mmecule- 5 2,394,905 Frey Feb. 12' 1946 FREDRICK M; SMITH- 2,403,879 Schulze et a1 July 9, 1940 ROBERT HANMER- 2,404,340 Zimmerman July 10, 1940 2,442,342 Burk et a1 June 1, 1948 REFERENCES CITED The following references are of record in the 10 file 01' this patent:

Claims (1)

1. AN IMPROVED PROCESS FOR CATALYTICALLY PRODUCING HIGH MOLECULAR WEIGHT ALKYL BENZENES, WHICH COMPRISES MIXING ALKYLATABLE BENZENE HYDROCARBONS AND OLEFIN-BEARING MATERIAL CONTAINING OLEFINS HAVING AT LEAST SEVEN AND NOT MORE THAN EIGHTEEN CARBON ATOMS PE MOLECULE WITH HYDROGEN FLUORIDE IN AN ALKYLATION ZONE; MAINTAINING A TEMPERATURE IN SAID ALKYLATION ZONE IN THE RANGE OF ABOUT 60 TO ABOUT 120*F.; MAINTAINING A PRESSURE IN SAID ALKYLATION ZONE SUFFICIENT TO PREVENT VAPORIZATION OF SAID HYDROGEN FLUORIDE; MAINTAINING THE RATE OF FEED OF SAID OLEFIN-BEARING MATERIAL AND SAID BENZENE HYDROCARBONS SUCH THAT THE RESIDENCE TIME IN SAID ALKYLATION ZONE IS IN THE RANGE OF ABOUT 5 TO ABOUT 60 MINUTES; MAINTAINING A MOL RATIO OF SAID BENZENE HYDROCARBONS TO SAID OLEFIN ENTERING SAID ALKYLATION ZONE IN THE RANGE OF ABOUT 15:1 TO ABOUT 2:1; INTRODUCING THE ENTIRE EFFLUENT REACTION MIXTURE WHICH CONTAINS POLYMERS OF SAID OLEFINS HAVING AT LEAST 7 CARBON ATOMS PER MOLECULE WHICH NORMALLY ARE DISSOLVED IN SAID HYDROGEN FLUORIDE AS WELL AS UNDESIRED POLYALKYL AROMATICS FROM SAID ALKYLATION ZONE TO A FRACTIONATION ZONE, REMOVING FROM THE UPPER AND PORTION OF SAID FRACTIONATION ZONE A SINGLE FRACTION COMPRISING HYDROGEN FLUORIDE AND UNREACTED BENZENE HYDROCARBONS, AND RECYCLING AT LEAST A PORTION OF SAID HYDROGEN FLUORIDE AND UNREACTED BENZENE HYDROCARBONS FRACTION TO SAID ALKYLATION ZONE; REMOVING FROM AN INTERMEDIATE PORTION OF SAID FRACTIONATION ZONE HYDROCARBON MATERIAL BOILING ABOVE SAID UNREACTED BENZENE HYDROCARBONS AND BOILING BELOW THE ALKYL BENZENE-BEARING MATERIAL, INTRODUCING THE REMAINING HIGHER BOILING ALKYL BENZENE-BEARING MATERIAL FROM SAID FRACTIONATION ZONE TO ANOTHER FRACTIONATION ZONE, REMOVING AN ALKYL BENZENE FRACTION FROM SAID HIGHER-BOILING ALKYL BENZENE-BEARING MATERIAL, AND RECYCLING AT LEAST A PORTION OF THE REMAINING HIGHER-BOILING MATERIAL WHICH CONTAINS THE SAID POLYMERS OF SAID OLEFINS AND SAID UNDESIRED POLYALKYL AROMATICS TO SAID ALKYLATION ZONE WHEREIN DEPOLYMERIZATION OF SAID POLYMERS OF SAID OLEFINS AND SIDE-CHAIN TRANSFER FROM THE SAID UNDESIRED POLYALKYL AROMATICS RESULTING IN DESIRABLE ALKYLATION OF BENZENE BY THE DEPOLYMERIZED OLEFINS AND THE SIDE-CHAINS FROM THE UNDESIRED POLYALKYL BENZENES IS CAUSED TO OCCUR SIMULTANEOUSLY WITH THE ALKYLATION IN SAID ALKYLATION ZONE OF THE BENZENE BY SAID OLEFINS HAVING AT LEAST 7 CARBON ATOMS PER MOLECULE.
US753562A 1947-06-09 1947-06-09 Production of alkyl benzenes Expired - Lifetime US2507766A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US753562A US2507766A (en) 1947-06-09 1947-06-09 Production of alkyl benzenes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US753562A US2507766A (en) 1947-06-09 1947-06-09 Production of alkyl benzenes

Publications (1)

Publication Number Publication Date
US2507766A true US2507766A (en) 1950-05-16

Family

ID=25031176

Family Applications (1)

Application Number Title Priority Date Filing Date
US753562A Expired - Lifetime US2507766A (en) 1947-06-09 1947-06-09 Production of alkyl benzenes

Country Status (1)

Country Link
US (1) US2507766A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1093340B (en) * 1956-07-18 1960-11-24 Huels Chemische Werke Ag Process for the preparation of alkylated aromatic hydrocarbons
EP0137288A1 (en) * 1983-09-22 1985-04-17 Uop Inc. Integrated HF regeneration in aromatic hydrocarbon alkylation process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2275312A (en) * 1938-06-29 1942-03-03 E I Du Pont De Nemorus & Compa Process of nuclear alkylation in the presence of hydrofluoric acid
US2349211A (en) * 1941-10-11 1944-05-16 Shell Dev Alkylation process
US2394905A (en) * 1942-02-19 1946-02-12 Phillips Petroleum Co Alkylation of benzene
US2403879A (en) * 1944-03-10 1946-07-09 Phillips Petroleum Co Process of manufacture of aviation gasoline blending stocks
US2404340A (en) * 1945-07-19 1946-07-16 Universal Oil Prod Co Production of high antiknock fuel
US2442342A (en) * 1942-11-30 1948-06-01 Standard Oil Co Process of making isopropyl benzene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2275312A (en) * 1938-06-29 1942-03-03 E I Du Pont De Nemorus & Compa Process of nuclear alkylation in the presence of hydrofluoric acid
US2349211A (en) * 1941-10-11 1944-05-16 Shell Dev Alkylation process
US2394905A (en) * 1942-02-19 1946-02-12 Phillips Petroleum Co Alkylation of benzene
US2442342A (en) * 1942-11-30 1948-06-01 Standard Oil Co Process of making isopropyl benzene
US2403879A (en) * 1944-03-10 1946-07-09 Phillips Petroleum Co Process of manufacture of aviation gasoline blending stocks
US2404340A (en) * 1945-07-19 1946-07-16 Universal Oil Prod Co Production of high antiknock fuel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1093340B (en) * 1956-07-18 1960-11-24 Huels Chemische Werke Ag Process for the preparation of alkylated aromatic hydrocarbons
EP0137288A1 (en) * 1983-09-22 1985-04-17 Uop Inc. Integrated HF regeneration in aromatic hydrocarbon alkylation process

Similar Documents

Publication Publication Date Title
US4051191A (en) Solid phosphoric acid catalyzed alkylation of aromatic hydrocarbons
US2404340A (en) Production of high antiknock fuel
US4140622A (en) Process to reduce the benzene content of gasoline
US2564072A (en) Alkylation process
US2338711A (en) Alkylation of aromatics
US4225737A (en) Alkylation process
US2372320A (en) Hydrocarbon alkylation process
EP0046678B2 (en) Process for continuous production of cumene and/or diisopropylbenzene
US2395198A (en) Alkylation and olefin recovery process
US2476750A (en) Process for producing motor fuel by alkylation
US2507766A (en) Production of alkyl benzenes
US2432482A (en) Alkylation process
US4220806A (en) Plural stages of hydrofluoric acid alkylation utilizing separated acid phase as catalyst in the subsequent stage
US4237328A (en) Process for HF-catalyzed alkylation of aromatic hydrocarbons
EP0154317B1 (en) Hf alkylation with product recycle employing two reactors
US2293705A (en) Treatment of paraffin hydrocarbons
US5345027A (en) Alkylation process using co-current downflow reactor with a continuous hydrocarbon phase
EP0873291B1 (en) Process for manufacturing ethylbenzene or cumene
US2382506A (en) Olefin recovery process
US2534072A (en) Production of alkyl benzenes
US3998903A (en) Alkylation with separate butene streams including isobutylene
US4237327A (en) Process for HF-catalyzed alkylation of aromatic hydrocarbons
US2382067A (en) Alkylation
US2818459A (en) Alkylation of paraffin hydrocarbons
US2507765A (en) Production of alkyl benzenes